Fungicide mixtures based on pyridine carboxamides

ABSTRACT

Fungicidal mixtures comprise as active components 
     a) an amide compound of the formula I 
     
       
         A—CO—NR 1 R 2   I 
       
     
      in which 
     A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered heterocycle which has from 1 to 3 hetero atoms selected from O, N and S; 
     where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, CHF 2 , CF 3 , alkoxy, haloalkoxy, alkylthio, alkylsulfynyl and alkylsulfonyl; 
     R 1  is a hydrogen atom; 
     R 2  is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, where the aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, independently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the amidic phenyl group may or may not be condensed with a saturated 5-membered ring which may or may not be substituted by one or more alkyl groups and/or may have a hetero atom selected from O and S, and 
     b) fungicides from the group of the dicarboximides and/or 
     c) pyrimidine derivatives of the formula III                    
      in which R is methyl, propyn-1-yl or cyclopropyl, and/or 
     d) fludioxinil or fenpiclonil and/or 
     e) captan, captafol or folpet and/or 
     f) fluazinam and/or 
     g) dichlofluanid or tolylfluanid 
     in a synergistically effective amount.

This application is a 371 of PCT/EP98/08231, filed Dec. 15, 1998.

The present invention relates to fungicidal mixtures for controllingharmful fungi, which mixtures comprise amide compounds of the formula I

A—CO—NR¹R²  (I)

in which

A is an aryl group or an aromatic or non-aromatic, 5- or 6-memberedheterocycle which has from 1 to 3 hetero atoms selected from O, N and S;

where the aryl group or the heterocycle may or may not have 1, 2 or 3substituents which are selected, independently of one another, fromalkyl, halogen, CHF₂, CF₃, alkoxy, haloalkoxy, alkylthio, alkylsulfynyland alkylsulfonyl;

R¹ is a hydrogen atom;

R² is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3substituents which are selected from alkyl, alkenyl, alkynyl, alkoxy,alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy,cycloalkenyloxy, phenyl and halogen, where the aliphatic andcycloaliphatic radicals may be partially or fully halogenated and/or thecycloaliphatic radicals may be substituted by from 1 to 3 alkyl groupsand where the phenyl group may have from 1 to 5 halogen atoms and/orfrom 1 to 3 substituents which are selected, independently of oneanother, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio andhaloalkylthio, and where the amidic phenyl group may or may not becondensed with a saturated 5-membered ring which may or may not besubstituted by one or more alkyl groups and/or may have a hetero atomselected from O and S, and

b) fungicides of the group of the dicarboximides and/or

c) a pyrimidine derivative of the formula III,

 in which R is methyl, propyn-1-yl or cyclopropyl, and/or

d) at least one active ingredient of the formula IV or V,

 and/or

e) a phthalimide derivative selected from the group consisting of thecompounds VIa, VIb and VII

 and/or

f) a dinitroaniline of the formula VIII

 and/or

g) an arylsulfamide of the formula IX a or IXb

in a synergistically effective amount.

WO 97/08952 describes fungicidal mixtures which, in addition tocompounds of the formula I, also comprise fenazaquin as furthercomponents. These are described as being very effective againstBotrytis.

The amide compounds of the formula I are known per se and are describedin the literature (EP-A 545 099).

Fungicides from the group of the dicarboximides are known to the personskilled in the art and are commercially available.

Also known are the pyrimidine derivatives III, their preparation andtheir activity against harmful fungi [R=methyl: DD-A 151 404 (commonname: pyrimethanil); R=1-propynyl: EP-A 224 339 (common name:mepanipyrim); R=cyclopropyl: EP-A 310 550].

The compound IV is known from K. Gehmann, R. Nyfeler, A. J. Leadbeater,D. Nevill and D. Sozzi, Proceedings of the Brighton Crop ProtectionConference, Pests and Diseases 1990, Vol. 2, p. 399 (common name:fludioxinil) and is commercially available from Novartis.

The compound V is known from D. Nevill, R. Nyfeler, D. Sozzi,Proceedings of the Brighton Crop Protection Conference, Pests andDiseases 1988, Vol. 1, p. 65 (common name: fenpiclonil).

U.S. Pat. Nos. 2,553,770; 2,553,771; 2,553,776 describe the compoundsVIa (common name: captan) and VII (common name: folpet), theirpreparation and their activity against harmful fungi. The compound VIb(common name: captafol) is described in Phytopathology 52(1962), 52,754.

Likewise, the compound VIII, its preparation and its use (CAS RN79622-59-6, common name: fluazinam) are described in the literature.

The compounds IXa and IXb are known under the common names dichlofluanidand tolylfluanid, respectively, and are described in the German patent1193498.

It is an object of the present invention to provide mixtures which havean improved activity against harmful fungi combined with a reduced totalamount of active ingredients applied (synergistic mixtures), with a viewto reducing the application rates and to improving the activity spectrumof the known compounds.

We have found that this object is achieved by the mixtures defined atthe outset. Moreover, we have found that better control of harmful fungiis possible by applying the compounds I and the compounds II to VIIIsimultaneously, that is either together or separately, or by applyingthe compounds I and the compounds II to VIII in succession than when thecompounds I or II to VIII are applied on their own.

The mixtures according to the invention have synergistic action and aretherefore particularly suitable for controlling harmful fungi, inparticular of Botrytis species.

In the context of the present invention, halogen is fluorine, chlorine,bromine and iodine and is in particular fluorine, chlorine and bromine.

The term “alkyl” includes straight-chain and branched alkyl groups.These are preferably straight-chain or branched C₁-C₁₂-alkyl and inparticular C₁-C₆-alkyl groups. Examples of alkyl groups are alkyl suchas, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl,2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl,1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an alkyl group as defined above which is partially or fullyhalogenated by one or more halogen atoms, in particular by fluorine andchlorine. Preferably, there are from 1 to 3 halogen atoms present, andthe difluoromethyl or the trifluoromethyl group is particularlypreferred.

The above statements for the alkyl group and the haloalkyl group applyin a corresponding manner to the alkyl and haloalkyl groups in alkoxy,haloalkoxy, alkylthio, haloalkylthio, alkylsulfynyl and alkylsulfonyl.

The alkenyl group includes straight-chain and branched alkenyl groups.These are preferably straight-chain or branched C₃-C₁₂-alkenyl groupsand in particular C₃-C₆-alkenyl groups. Examples of alkenyl groups are2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl,2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and1-ethyl-2-methyl-2-propenyl, in particular 2-propenyl, 2-butenyl,3-methyl-2-butenyl and 3-methyl-2-pentenyl.

The alkenyl group may be partially or fully halogenated by one or morehalogen atoms, in particular by fluorine or chlorine. The alkenyl grouppreferably has from 1 to 3 halogen atoms.

The alkynyl group includes straight-chain and branched alkynyl groups.These are preferably straight-chain and branched C₃-C₁₂-alkynyl groupsand in particular C₃-C₆-alkynyl groups. Examples of alkynyl groups are2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl,1,2-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.

The above statements for the alkenyl group and its halogen substituentsand for the alkynyl group apply in a corresponding manner to alkenyloxyand alkynyloxy.

The cycloalkyl group is preferably a C₃-C₆-cycloalkyl group, such ascyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. If the cycloalkylgroup is substituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicalsas substituents.

Cycloalkenyl is preferably a C₄-C₆-cycloalkenyl group, such ascyclobutenyl, cyclopentenyl or cyclohexenyl. If the cycloalkenyl groupis substituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

A cycloalkoxy group is preferably a C₅-C₆-cycloalkoxy group, such ascyclopentyloxy or cyclohexyloxy. If the cycloalkoxy group issubstituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

The cycloalkenyloxy group is preferably a C₅-C₆-cycloalkenyloxy group,such as cyclopentyloxy or cyclohexyloxy. If the cycloalkenyloxy group issubstituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

Aryl is preferably phenyl.

If A is a phenyl group, this may have one, two or three of theabovementioned substituents in any position. These substituents arepreferably selected, independently of one another, from alkyl,difluoromethyl, trifluoromethyl and halogen, in particular chlorine,bromine and iodine. Particularly preferably, the phenyl group has asubstituent in the 2-position.

If A is a 5-membered heterocycle, it is in particular a furyl,thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl orthiadiazolyl radical or the corresponding dihydro or tetrahydroderivatives thereof. Preference is given to a thiazolyl or pyrazolylradical.

If A is a 6-membered heterocycle, it is in particular a pyridyl radicalor a radical of the formula:

in which one of the radicals X and Y is O, S or NR²³, where R²³ is H oralkyl, and the other of the radicals X and Y is CH₂, S, SO, SO₂ or NR²³.The dotted line means that a double bond may or may not be present.

The 6-membered aromatic heterocycle is particularly preferably a pyridylradical, in particular a 3-pyridyl radical, or a radical of the formula

in which X is CH₂, S, SO or SO₂.

The abovementioned heterocyclic radicals may or may not have 1, 2 or 3of the abovementioned substituents, where these substituents arepreferably selected, independently of one another, from alkyl, halogen,difluoromethyl or trifluoromethyl.

A is particularly preferably a radical of the formulae:

in which R³, R⁴, R⁶, R⁷, R⁸ and R⁹ independently of one another arehydrogen, alkyl, in particular methyl, halogen, in particular chlorine,CHF₂ or CF₃.

The radical R¹ in the formula I is preferably a hydrogen atom.

The radical R² in the formula I is preferably a phenyl radical. R²preferably has at least one substituent which is particularly preferablyin the 2-position. The substituent (or the substituents) is (are)preferably selected from the group consisting of alkyl, cycloalkyl,cycloalkenyl, halogen or phenyl.

The substituents of the radical R² may in turn be substituted again. Thealiphatic or cycloaliphatic substituents may be partially or fullyhalogenated, in particular fluorinated or chlorinated. They preferablyhave 1, 2 or 3 fluorine or chlorine atoms. If the substituent of theradical R² is a phenyl group, this phenyl group may preferably besubstituted by from 1 to 3 halogen atoms, in particular chlorine atoms,and/or by a radical which is preferably selected from alkyl and alkoxy.Particularly preferably, the phenyl group is substituted with a halogenatom in the p-position, i.e. the particularly preferred substituent ofthe radical R² is a p-halogen-substituted phenyl radical. The radical R²may also be condensed with a saturated 5-membered ring, where this ringfor its part may have from 1 to 3 alkyl substituents.

R² is in this case, for example, indanyl, thiaindanyl and oxaindanyl.Preference is given to indanyl and 2-oxaindanyl which are attached tothe nitrogen atom in particular via the 4-position.

According to a preferred embodiment, the composition according to theinvention comprises as amide compound a compound of the formula I inwhich A is as defined below:

phenyl, pyridyl, dihydropyranyl, dihydrooxathiynyl,dihydrooxathiynyloxide, dihydrooxathiynyldioxide, furyl, thiazolyl,pyrazolyl or oxazolyl, where these groups may have 1, 2 or 3substituents which are selected, independently of one another, fromalkyl, halogen, difluoromethyl and trifluoromethyl.

According to a further preferred embodiment, A is one of the followinggroups:

pyridin-3-yl, which may or may not be substituted in the 2-position byhalogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio,methylsulfynyl or methylsulfonyl;

phenyl, which may or may not be substituted in the 2-position by methyl,trifluoromethyl, chlorine, bromine or iodine;

2-methyl-5,6-dihydropyran-3-yl;

2-methyl-5,6-dihydro-1,4-oxathiyn-3-yl or the 4-oxide or 4,4-dioxidethereof;

2-methylfuran-3-yl, which may or may not be substituted in the 4- and/or5-position by methyl;

thiazol-5-yl, which may or may not be substituted in the 2-and/or4-position by methyl, chlorine, difluoromethyl or trifluoromethyl;

thiazol-4-yl, which may or may not be substituted in the 2-and/or5-position by methyl, chlorine, difluoromethyl or trifluoromethyl;

1-methylpyrazol-4-yl, which may or may not be substituted in the 3-and/or 5-position by methyl, chlorine, difluoromethyl ortrifluoromethyl; or

oxazol-5-yl, which may or may not be substituted in the 2- and/or4-position by methyl or chlorine.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formula Iin which R² is a phenyl group which may or may not be substituted by 1,2 or 3 of the abovementioned substituents.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formula Iin which R² is a phenyl group which has one of the followingsubstituents in the 2-position:

C₃-C₆-alkyl, C₅-C₆-cycloalkenyl, C₅-C₆-cycloalkyloxy, cycloalkenyloxy,where these groups may be substituted by 1, 2 or 3 C₁-C₄-alkyl groups,

phenyl, which is substituted by from 1 to 5 halogen atoms and/or from 1to 3 groups which are selected, independently of one another, fromC₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio and C₁-C₄-haloalkylthio,

indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3C₁-C₄-alkyl groups.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formulaIa,

in which

A is

X is methylene, sulfur, sulfynyl or sulfonyl (SO₂),

R³ is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine oriodine,

R⁴ is trifluoromethyl or chlorine,

R⁵ is hydrogen or methyl,

R⁶ is methyl, difluoromethyl, trifluoromethyl or chlorine,

R⁷ is hydrogen, methyl or chlorine,

R⁸ is methyl, difluoromethyl or trifluoromethyl,

R⁹ is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine,

R¹⁰ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or halogen.

According to a particularly preferred embodiment, the compositionscomprise as amide compound a compound of the formula Ib

in which

R⁴ is halogen and

R¹¹ is phenyl which is substituted by halogen.

Useful amide compounds of the formula I are mentioned in EP-A-545 099and 589 301 which are incorporated herein in their entirety byreference.

The preparation of the amide compounds of the formula I is known, forexample, from EP-A-545 099 or 589 301 or can be carried out by similarprocesses.

Preferred substituents R²¹ and R²² are hydrogen, F, Cl, methyl, ethyl,methoxy, thiomethyl and N-methylamino. R³ and R⁴ together may also forma grouping ═O.

Preferred fungicides of the dicarboximide type are the compounds IIa toIId:

II.a: ethyl(RS)-3-(3,5-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate

II.b:3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine1-carboxamide

 or

II.c: N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide

 or

II.d:(RS)-3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione

These compounds are commercially available as fungicidally activeingredients and are described in the literature as follows:

II.a (common name: chlozolinate): CAS RN [84332-86-5], DE-A 29 06 574;

II.b (common name: iprodione): CAS RN [36734-19-7], U.S. Pat. No.3,755,350;

II.c (common name: procymidone): CAS RN [32809-16-8], U.S. Pat. No.3,903,090;

II.d (common name: vinclozoline): CAS RN [50471-44-8], DE-A 22 07 576].

To unfold the synergistic activity, even a small amount of the amidecompound of the formula I is sufficient. Preference is given toemploying amide compound and active ingredient of the formula II and/orIII to IX in a weight ratio in the range of from 50:1 to 1:50, inparticular from 10:1 to 1:10. It is also possible here to employ ternarymixtures which, in addition to amide compounds I, comprise bothcompounds II and one or more compounds III to IX. In such mixtures, themixing ratio of the compounds II and III to IX with each other isusually in the range of from 50:1 to 1:50, preferably from 10:1 to 1:10.

Owing to the basic character of their nitrogen atoms, the compounds III,IV, V and VIII are capable of forming salts or adducts with inorganic ororganic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid and alkanoic acids,such as acetic acid, trifluoroacetic acid, trichloroacetic acid andpropionic acid, and also glycolic acid, thiocyanic acid, lactic acid,succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid,alkylsulfonic acids (sulfonic acids having straight-chain or branchedalkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids oraryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl,which carry one or two sulfo groups), alkylphosphonic acids (phosphonicacids having straight-chain or branched alkyl radicals of 1 to 20 carbonatoms), arylphosphonic acids or aryldiphosphonic acids (aromaticradicals, such as phenyl and naphthyl, which carry one or two phosphonicacid radicals), it being possible for the alkyl or aryl radicals tocarry further substituents, eg. p-toluenesulfonic acid, salicylic acid,p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid,etc.

Suitable metal ions are, in particular, the ions of the elements of thefirst to eighth sub-group, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and furthermore of the second main group,in particular calcium and magnesium, and of the third and fourth maingroup, in particular aluminum, tin and lead. The metals can exist in thevarious valencies which they can assume.

When preparing the mixtures, it is preferred to employ the pure activeingredients I and II to IX, to which further active ingredients againstharmful fungi or other pests, such as insects, arachnids or nematodes,or else herbicidal or growth-regulating active ingredients orfertilizers, can be admixed.

The mixtures of the compounds I and II and/or III to IX, or thecompounds I and II and/or III to IX used simultaneously, jointly orseparately, exhibit outstanding activity against a wide range ofphytopathogenic fungi, in particular from the classes of theAscomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some ofthem act systemically and can therefore be employed as foliar- andsoil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as cotton, vegetable species (eg.cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass,oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine,wheat, ornamentals, sugar cane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawns, Ustilago species in cereals and sugar cane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinerea (gray mold) in strawberries, vegetables,ornamentals and grapevines, Cercospora arachidicola in groundnuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Plasmopara viticola in grapevines, Pseudoperonospora species in hops andcucumbers, Alternaria species in vegetables and fruit, Mycosphaerellaspecies in bananas and Fusarium and Verticillium species.

The mixtures according to the invention may particularly preferably beemployed for controlling Botrytis species in crops of grapevines andvegetables, and also in ornamentals.

The compounds I and II and/or III to IX can be applied simultaneously,either together or separately, or in succession, the sequence, in thecase of separate application, generally not having any effect on theresult of the control measures.

Depending on the kind of effect desired, the application rates of themixtures according to the invention are, in particular in agriculturalcrop areas, from 0.01 to 8 kg/ha, preferably 0.1 to 5 kg/ha, inparticular 0.2 to 3.0 kg/ha.

The application rates of the compounds I are from 0.01 to 2.5 kg/ha,preferably 0.05 to 2.5 kg/ha, in particular 0.1 to 1.0 kg/ha.

Correspondingly, in the case of the compounds II and/or III to IX, theapplication rates are from 0.01 to 10 kg/ha, preferably 0.05 to 5 kg/ha,in particular 0.05 to 2.0 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, inparticular 0.01 to 50 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II and/or III to IX or of themixtures of the compounds I and II and/or III to IX is effected byspraying or dusting the seeds, the plants or the soils before or aftersowing of the plants, or before or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I and II and/or III to IX, can be formulated for example inthe form of ready-to-spray solutions, powders and suspensions or in theform of highly concentrated aqueous, oily or other suspensions,dispersions, emulsions, oil dispersions, pastes, dusts, materials forbroadcasting or granules, and applied by spraying, atomizing, dusting,broadcasting or watering. The use form depends on the intended purpose;in any case, it should ensure as fine and uniform as possible adistribution of the mixture according to the invention.

The formulations are prepared in a known manner, eg. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible also to use other organicsolvents as auxiliary solvents if water is used as the diluent. Suitableauxiliaries for this purpose are essentially: solvents such as aromatics(eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg.mineral oil fractions), alcohols (eg. methanol, butanol), ketones (eg.cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water;carriers such as ground natural minerals (eg. kaolins, clays, talc,chalk) and ground synthetic minerals (eg. finely divided silica,silicates); emulsifiers such as nonionic and anionic emulsifiers (eg.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates) and dispersants such as lignosulfite waste liquors andmethylcellulose.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, eg. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols,or of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, laurylalcohol polyglycol ether acetate, sorbitol esters, lignosulfite wasteliquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor jointly grinding the compounds I or II and/or III to IX, or themixture of the compounds I and II and/or III to IX, with a solidcarrier.

Granules (eg. coated granules, impregnated granules or homogeneousgranules) are usually prepared by binding the active ingredient, oractive ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials andfertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably 0.5 to 90% by weight, of one of the compounds I and II and/orIII to IX or of the mixture of the compounds I and II and/or III to IX.The active ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum or EPLC).

The compounds I and II and/or III to IX, the mixtures, or thecorresponding formulations, are applied by treating the harmful fungi,their habitat, or the plants, seeds, soils, areas, materials or spacesto be kept free from them with a fungicidally effective amount of themixture, or of the compounds I and II and/or III to IX in the case ofseparate application.

Application can be effected before or after infection by the harmfulfungi.

Examples of such preparations comprising the active ingredients are:

I. A solution of 90 parts by weight of the active ingredients and 10parts by weight of N-methylpyrrolidone; this solution is suitable foruse in the form of microdrops;

II. A mixture of 20 parts by weight of the active ingredients, 80 partsby weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol ofethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenzenesulfonate, 5 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil; adispersion is obtained by finely distributing the solution in water;

III. An aqueous dispersion of 20 parts by weight of the activeingredients, 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxideand 1 mol of castor oil;

IV. An aqueous dispersion of 20 parts by weight of the activeingredients, 25 parts by weight of cyclohexanol, 65 parts 30 by weightof a mineral oil fraction of boiling point 210 to 280° C., and 10 partsby weight of the adduct of 40 mol of ethylene oxide and 1 mol of castoroil;

V. A mixture, ground in a hammer mill, of 80 parts by weight of theactive ingredients, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-1-sulfonate, 10 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel; a spray mixture is obtained by finelydistributing the mixture in water;

VI. An intimate mixture of 3 parts by weight of the active ingredientsand 97 parts by weight of finely divided kaolin; this dust comprises 3%by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of the activeingredients, 92 parts by weight of pulverulent silica gel and 8 parts byweight of paraffin oil which had been sprayed onto the surface of thissilica gel; this formulation imparts good adhesion to the activeingredient;

VIII. A stable aqueous dispersion of 40 parts by weight of the activeingredients, 10 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate, 2 parts by weight of silica gel and48 parts by weight of water; this dispersion may be diluted further;

IX. A stable oily dispersion of 20 parts by weight of the activeingredients, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycolether, 20 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate and 88 parts by weight of a paraffinicmineral oil.

USE EXAMPLE

The synergistic activity of the mixtures according to the invention canbe demonstrated by the following experiments:

The active ingredients, separately or together, are formulated as a 10%emulsion in a mixture of 63% by weight of cyclohexanone and 27% byweight of emulsifier, and diluted with water to the desiredconcentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The efficacy(W) is calculated as follows using Abbot's formula:

W=(1−α)·100/β

α corresponds to the fungal infection of the treated plants in % and

β corresponds to the fungal infection of the untreated (control) plantsin %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the mixtures of the active ingredients weredetermined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)]and compared with the observed efficacies.

Colby formula: E=x+y−x·y/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active ingredients A and B at the concentrations aand b

x efficacy, expressed in % of the untreated control, when using activeingredient A at a concentration of a

y efficacy, expressed in % of the untreated control, when using activeingredient B at a concentration of b

Use Example 1

Activity Against Botrytis cinerea on Bell Pepper Leaves

Bell pepper seedlings of the variety “Neusiedler Ideal Elite” were,after 4-5 leaves were well developed, sprayed to runoff point with anaqueous preparation of active ingredient which had been prepared from astock solution comprising 10% of active ingredient, 63% of cyclohexanoneand 27% of emulsifier. The next day, the treated plants were inoculatedwith a spore suspension of Botrytis cinerea containing 1.7×10⁶ sporesper ml of a 2% strength aqueous Biomalz solution. The test plants weresubsequently placed in a climatized chamber with high atmospherichumidity at 22-24° C. After 5 days, the extent of the fungal infectionon the leaves could be determined visually in %.

The compounds of the formula I used were the following components:

The results are shown in Tables 1 and 2 below.

TABLE 1 Concentration of active ingredient in Active the spray liquorEfficacy in % of the Ex. ingredient in ppm untreated control 1Cuntreated 0 (99% infection) 0 2C Compound I.1 31 78 16 67 8 11 3CCompound I.2 31 67 16 44 8 44 4C Compound VIa 31 0 16 0 8 0 5C CompoundVII 31 0 16 0 8 0 6C Compound IXa 31 0 16 0 8 0

TABLE 2 Mixtures according to the invention observed calculated Ex.(content in ppm) efficacy efficacy*⁾ 7 31 ppm I.1 + 97 78 31 ppm VIa 8 8ppm I.1 + 30 11 8 ppm VIa 9 31 ppm I.2 + 100 67 31 ppm VIa 10 16 ppmI.2 + 70 44 16 ppm VIa 11 31 ppm I.1 + 90 78 31 ppm VII 12 8 ppm I.1 +39 11 8 ppm VII 13 31 ppm I.2 + 93 67 31 ppm VII 14 16 ppm I.2 + 90 4416 ppm VII 15 8 ppm I.2 + 90 44 8 ppm VII 16 31 ppm I.1 + 95 78 31 ppmIXa 17 16 ppm I.1 + 90 67 16 ppm IXa 18 31 ppm I.2 + 100 67 31 ppm IXa19 16 ppm I.2 + 99 44 16 ppm IXa 20 8 ppm I.2 + 90 44 8 ppm IXa*⁾calculated using Colby's formula

The test results show that for all mixing ratios the observed efficacyis higher than the efficacy which had been calculated beforehand usingColby's formula.

Use Example 2

Activity Against Botryis cinerea on Bell Peppers

Disks of green bell peppers were sprayed to runoff point with an aqueouspreparation of active ingredient which had been prepared from a stocksolution comprising 10% of active ingredient, 63% of cyclohexanone and27% of emulsifier. 2 hours after the spray coating had dried on, thefruit disks were inoculated with a spore suspension of Botrytis cinereacontaining 1.7×106 spores per ml of a 2% strength Biomalz solution. Theinoculated fruit disks were subsequently incubated in humid chambers at18° C. for 4 days. The Botrytis infection on the diseased fruit diskswas then evaluated visually.

The results are shown on tables 3 and 4 below.

TABLE 3 Concentration of active ingredient Efficacy in % of Active inthe spray the untreated Ex. ingredient liquor in ppm control 21Cuntreated 0 (100% infection) 0 22C Compound I.1 31 0 16 0 23C CompoundI.2 31 20  16 0 24C Compound IV 31 0 16 0 25C Compound VIa 31 0 26CCompound VII 31 0 27C Compound VIII 31 0 16 0

TABLE 4 Mixtures according to the invention observed calculated Ex.(content in ppm) efficacy efficacy*⁾ 28 31 ppm I.1 + 50 0 31 ppm IV 2916 ppm I.1 + 20 0 16 ppm IV 30 31 ppm I.2 + 70 20 31 ppm IV 31 16 ppmI.2 + 20 0 16 ppm IV 32 31 ppm I.2 + 50 20 31 ppm IVa 33 31 ppm I.2 + 4020 31 ppm VII 34 31 ppm I.1 + 30 0 31 ppm VIII 35 16 ppm I.2 + 20 0 16ppm VIII *⁾calculated using Colby's formula

The test results show that for all mixing ratios the observed efficacyis higher than the efficacy which had been calculated beforehand usingColby's formula.

We claim:
 1. A fungicidal composition comprising as active components a)an amide compound of formula I A—CO—NR¹R²  I  in which A is pyridylwhich is unsubstituted or carries 1, 2 or 3 substituents selected fromalkyl, halogen, CHF₂, CF₃, alkoxy, haloalkoxy, alkylthio, alkylsulfynyland alkylsulfonyl; R¹ is a hydrogen atom; R² is phenyl which isunsubstituted or carries 1, 2 or 3 substituents selected from alkyl,alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl,cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, wherethe aliphatic and cycloaliphatic radicals are unsubstituted or arepartially or fully halogenated, and the cycloaliphatic radicalsoptionally carry from 1 to 3 alkyl groups, and where the phenyl group isunsubstituted or carries from 1 to 5 halogen atoms and/or from 1 to 3substituents selected from alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio and haloalkylthio, and where the amidic phenyl group isoptionally condensed with a saturated 5-membered ring which isunsubstituted or substituted by one or more alkyl groups; and b) atleast one fungicide from the group of dicarboximides, and optionally adinitroaniline of formula VIII

wherein the active components (a) and (b), and optionally thedinitroaniline of formula VIII, are present in synergistically effectiveamounts.
 2. The composition defined in claim 1, wherein A is pyridylwhich is unsubstituted or carries 1, 2 or 3 substituents selected fromalkyl, halogen, difluoromethyl and trifluoromethyl.
 3. The compositiondefined in claim 1, wherein A is pyridin-3-yl, which is unsubstituted oris substituted in the 2-position by halogen, methyl, difluoromethyl,trifluoromethyl, methoxy, methylthio, methylsulfynyl or methylsulfonyl.4. A fungicidal mixture as claimed in one of the preceding claims, whichcomprises a compound of the formula I in which R² is a phenyl groupwhich may or may not be substituted by 1, 2 or 3 of the substituentsmentioned in claim
 1. 5. The composition defined in claim 1, where R² isa phenyl group which has one of the following substituents in the2-position: C₃-C₆-alkyl, C₅-C₆-cycloalkenyl, C₅-C₆-cycloalkyloxy,cycloalkenyloxy, where these groups are unsubstituted or substituted by1, 2 or 3 C₁-C₄-alkyl groups, phenyl which is substituted by from 1 to 5halogen atoms and/or from 1 to 3 radicals selected from C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio andC₁-C₄-haloalkylthio, or where R² is indanyl which is unsubstituted orsubstituted by 1, 2 or 3 C₁-C₄-alkyl groups.
 6. The composition definedin claim 1, wherein the amide compound is a compound of formula Ia

in which A is a radical A2

R⁴ is trifluoromethyl or chlorine, and R¹⁰ is C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkylthio or halogen.
 7. The composition defined in claim 1,wherein the amide compound is a compound of formula Ib

in which R⁴ is halogen and R¹¹ is phenyl which is substituted byhalogen.
 8. The composition defined in claim 1, wherein the amidecompound is selected from the group of


9. The composition defined in claim 1, wherein the one or moredicarboxyimide(s) is/are selected from the group of the compounds IIa toIId II.a: ethyl(RS)-3-(3,5-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate

II.b:3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide

II.c: N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide

 and II.d:(RS)-3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione


10. The composition defined in claim 1 which is conditioned in twoparts, a first part comprising the amide compound of formula I in asolid or liquid carrier, and a second part comprising at least onefungicide selected from the group of dicarboximides in a solid or liquidcarrier.
 11. The composition defined in claim 1, wherein the activecomponent (a) and the active component (b) are present in a weight ratioof from 50:1 to 1:50.
 12. The composition defined in claim 1, whereinthe active component (a) and the active component (b) are present in aweight ratio of from 10:1 to 1:10.
 13. A method for controlling harmfulfungi, which comprises treating the fungi, their habitat, or materials,plants, seeds, soils, areas or spaces to be protected against fungalattack with an effective amount of the composition defined in claim 1,wherein the active components are applied simultaneously, that is eithertogether or separately, or in succession.
 14. The method of claim 13,wherein the active component (a) is applied in an amount of from 0.01 to2.5 kg/ha.
 15. The method of claim 13, wherein the active component (b)is applied in an amount of from 0.01 to 10 kg/ha.
 16. The method ofclaim 13, wherein the active component (b) and the dinitroaniline offormula VIII are applied in an amount of from 0.01 to 10 kg/ha.